Epoxyorganofluorosilanes and amino-hydroxy derivatives thereof

ABSTRACT

The invention characterizes novel epoxy organo fluoro silanes wherein the fluorine is directly bonded to silicon.

United States Patent inventors Enrico J. Pepe Kenmore;

Bernard Kanner, Tonawanda, lboth of NY. 643,771

Apr. 6, 1967 Nov. 30, 1971 Union Carbide Corporation Originalapplication Oct. 3, 1963, Ser. No. 313,418, now Patent No. 3,334,121.Divided and this application Apr. 6, 1967, Ser. No. 643,771

Appl. No. Filed Patented Assignee US. Cl ..260/348SC, 260/448.2 B,117/72, 117/126 GE, 117/126 GS, 117/126GN Int. Cl C07f 7/12 [50] Fieldof Search 260/4482 B, 348 SC; 117/72 [5 6] References Cited UNITEDSTATES PATENTS 2,946,701 7/1960 Plueddemann 1 17/72 3,128,297 4/1964Kanner et a1. 260/4482 3,227,675 1/1966 Papalos 260/41 3,398,210 8/1968Plueddemann et al. 260/4482 FOREIGN PATENTS 1,061,321 7/1959 Germany260/348 Primary Examiner-Norma S. Milestone Attorneys-Paul A. Rose,Thomas 1. O'Brien, Eugene C.

Trautlein and Harrie M. Humphreys ABSTRACT: The invention characterizesnovel epoxy organo fluoro silanes wherein the fluorine is directlybonded to silicon.

invention are wherein Y is a monovalent hydrocarbon group free ofaliphatic unsaturation and containing an oxirane ring; R is a monovalenthydrocarbon group free of aliphatic unsaturation; X is fluorine or ahydrocarbyloxy group -OR; b is an integer having a value from zero to l;c is an integer having a value from l to 2; d is an integer having avalue from zero to l; the sum of c and d carbon is 2; when b is zerothen e is an integer having a value from 1 to about 6, and when b is Ithen (i) e. is an integer having a value from 2 to about 6 and theoxygen atom is separated from silicon by at least two carbon atoms ofthe CJ-l group and (ii) the oxirane ring in the Y group is separatedfrom the oxygen atom by at least one carbon atom.

The monovalent Y group contains carbon, hydrogen and an oxirane ringhaving the structure Preferably the Y group contains from three to aboutten carbon atoms. Illustrative of the Y groups are the following:

and the like.

The monovalent hydrocarbon group R, when bonded directly to silicon orwhen forming part of a hydrocarbyloxy group OR, is preferably onecontaining from one to about ten carbon atoms, for example, an alkyl,cycloalkyl aryl, alkaryl or aralkyl group such as methyl, ethyl,isobutyl, hexyl, 2-ethylhexyl, cyclopentyl, 2-ethylcyclohexyl, phenyl,tolyl, mesityl, cumy], beta-phenylethyl, naphthyl, and the like.

Illustrative of the compounds of this invention as represented byformula A are the following:

As used herein, C I-l C H and C H represent the phenyl, n-hexyl andethyl groups, respectively.

The stability of the compounds of formula A is unexpected in view of theknown reactivity of siliconhalogen bonds with oxirane rings. See forexample, Organosilicon Compounds by C. Eaborn, Academic Press, New York,l960, pp. 299-300.

The epoxyorganofluorosilanes of this invention (compounds of formula A)can be produced by a process which comprises the reaction in thepresence of a platinum catalyst of l a silane represented by the formulawherein R, X, c and dhave the meanings defined hereinabove withreference to formula A, and 2) an organic epoxide containing 21carbon-carbon double bond and represented by the formula ]h 0 2r whereinY, b and e have the meanings defined hereinabove with reference toformula A and when b is l the carbon-carbon double bond is in the C limoiety.

Illustrative of the silanes represented by formula B are CH; H lFz C HHiF O CHzCHzCHa CoHi:

F H A 1 5):

HSiCli wherein R and c have the meanings defined hereinabove withreference to formula A, f is an integer having a value from i to 2, andthe sum of c and f is 3, with aqueous hydrofluoric acid and recoveringas a product the fluorosilane of formula B wherein X is fluorine. Forexample, methyldifluorosilane can be prepared by mixingmethyldichlorosilane and hydrofluoric acid and separatingmethyldifuorosilane from the reaction mixture by fractionaldistillation.

The compounds of formula B wherein X is a hydrocarbyloxy group (OR) canbe prepared by the reaction of the corresponding compound of formula Bwherein X is fluorine with a relatively low boiling hydrocarbyloxysilane, preferably a tetraalkylsilicate or methyltrialkoxysilane. Thisprocess is conveniently carried out by mixing a compound of formula B,wherein X is fluorine, with a hydrocarbyloxy silane and heat ing themixture at a temperature between 20 C. and 200 C. until redistributionof one of the silicon bonded fluorine atoms with a silicon-bondedhydrocarbyloxy group has taken place. Under the above-describedconditions only one of the two fluorine atoms attached to silicon willbe replaced by a hydrocarbyloxy group. The redistribution reaction isgenerally completed within about 1 to 5 hours and the mixedfluorohydrocarbyloxy silane can be separated from the reaction mixtureby fractional distillation. For example, methylfluoroethoxy silane canbe prepared by mixing methyldifluorosilane and tetraethylsilicate,heating the mixture at its atmospheric pressure boiling point for about2 hours, and separating methylfluoroethoxysilane from the reactionmixture by fractional distillation.

Illustrative of the unsaturated epoxy organic compounds of formula Care:

0 g omomomo --CHCHzCH=CI-Ig platinum catalyst at a temperature betweenabout 20" C. and 150 C. for about 1 hour to 48 hours or longer.Preferred reaction conditions are a temperature from 35 C. to C. forfrom 1 hour to 24 hours. Where the silane of formula 8 is a gas, it canbe bubbled into a mixture of the unsaturated epoxyorganic compound offormula C and the platinum catalyst.

It is desirable to employ stoichiometric amounts of the reactants,although up to a 100 percent stoichiometic excess of either reactant canbe used.

Although other than the above-described reaction temperatures, reactantratios and reaction times can be employed, no significant advantage isachieved thereby.

The use of an inert solvent in the process for preparing the compoundsof formula A is not necessary but is often desirable in helping todissipate heat liberated by the exothermic reaction of the compounds offormula B with compounds of formula C. lllustrative organic solventswhich can be used if desired are aromatic hydrocarbons such as benzene,toluene, xylene, cumene, and tetrahydronaphthalene, aliphatichydrocarbons such as heptane, octane and petroleum ether, and etherssuch as diethyl ether, dibutyl ether, dioxane, tetrahydrofuran, ethyleneglycol dimethyl ether and diethylene glycol dimethyl ether, and thelike.

Where a solvent is employed a convenient reaction temperature is thenormal boiling point of the solvent-reactant mixture.

Platinum catalysts that are useful in the process for producingcompounds of formula A include platinum metal and platinum compoundssuch as chloroplatinic acid and tetraamine platinous chloride, Pt(NH;,Cl Where platinum metal is employed as a catalyst it can be used alonein a finely divided form or supported on a solid substrate such ascharcoal or gamma-alumina. When a platinum compound is used as thecatalyst it can be used alone or dissolved in an inert solvent such asethanol. When platinum metal on a solid support is employed as thecatalyst it is preferable to agitate the reaction mixture.

The amount of platinum catalyst employed can vary from about one partper million to 200 parts per million or greater based on the totalweight of the silane of formula B and unsaturated epoxy organic compoundof formula C. The preferred amount of catalyst is about one to about 20parts per million.

The epoxyorganofluorosilane product can be recovered from the reactionmixture by conventional procedures, generally by fractional distillationat atmospheric or reduced pressure.

The amino-hydroxy-organofluorosilanes of this invention are representedby the formula wherein Z is a monovalent hydrocarbon group free ofaliphatic unsaturation and containing the unit HA Ni.

R is a monovalent hydrocarbon group free of aliphatic unsaturation; b isan integer having a value from zero to 1; c is an integer having a valuefrom I to 2; g is an integer having a value from I to 2; the sum ofc andg is 3; when b is zero, then e is an integer having a value from 1 toabout 6, and when b is 1 then (i) is an integer having a value from 2 toabout 6 and the oxygen atom is separated from silicon by at least twocarbon atoms of the C l-l group and (ii) the OH substituent in the Zgroup is separated from the oxygen atom by at least two carbon atoms.

Thus the compounds of formula D are the derivatives obtained by thereaction of a secondary amine, R NH, with the epoxy group of a compoundof formula A, X in formula A being fluorine.

The monovalent group Z contains carbon, hydrogen and the unit Preferablythe Z group contains from three to about ten carbon atoms, exclusive ofcarbon atoms present in the -NR substituent.

Illustrative of the Z groups are the following:

HON

The monovalent hydrocarbon group R preferably contains from one to aboutten carbon atoms and is identical in structure with the group R asdefined with reference to formula A hereinabove.

The stability of the compounds of formula D is unexpected in view of theknown reactivity of hydroxy compounds with silicon-bonded halogen atoms,particularly in the presence of halogen halide acceptors. See forexample Organosilicon Compounds by C Eaborn, Academic Press, New York,1960, pages 288-293.

The compounds of formula D can be produced by a process which comprisesthe reaction of an epoxyorganofluorosilane of formula A hereinabove,where X is fluorine, with a secondary amine represented by the formula RNH, wherein R has the meaning defined hereinabove. The Thenitrogen-hydrogen bond in the secondary amine reacts with the oxiranering of the epoxy-organofluorosilane to produce a grouping having aconfiguration The addition reaction of the secondary amine and thelepoxy-organofluorosilane generally produces a mixture of the twopossible isomers. However when (l the oxirane ring is in a terminalposition in the Y group. that is when the epoxy group has the structure'C r--CH and (2) the oxirane ring is not directly bonded to an aromaticring, the principal reaction product is the isomer having the structureand only relatively small amounts of the other isomer are obtained.

The reaction of the epoxyorganofluorosilane and the secondary amine canbe carried out by mixing the reactants and heating the mixture at atemperature between 25 C. and l50 C. for about 1 to about 5 hours. Thecompound of formula I) can then be separated from the reaction mixtureby fractional distillation. The mole ratio of secondary amine toepoxyorganofluorosilane can vary from about 1:1 to about 3:1. Thereaction is preferably carried out under anhydrous conditions.

Relatively lower reaction temperatures are required when the startingepoxyorganofluorosilane of formula A is one in which b is one. When b iszero in the compound of formula A, relatively higher reactiontemperatures are required.

An inert solvent is generally not required in the reaction of thesecondary amine with the epoxyorganofluorosilane. However, theillustrative inert solvents described hereinabove (with reference to thereaction of compounds of formula B with compounds of formula C) can beused if desired.

The reaction of the secondary amine with the oxirane ring of thecompound of formula A is accelerated by adding to the reaction mixture asmall amount (less than one weight percent) of an organic hydroxycompound, preferably an alkanol such as ethanol, isopropanol or butanol.

Illustrative of the secondary amines which can be used in the precessfor producing compounds of formula D are:

0 H: C HzCuHs CHa CgHs, and the llk The reaction ofepoxyorganofluorosilanes (a), (b), (e), (f) and (g) hereinabove with,respectively, secondary amines (a'), (b), (e'), (f and (g) hereinaboveyields, respectively, the following illustrative compounds of formula D:

(a-a') on (3H, (mmnN-cmcncmo cHmsm 0H CH: (bb') (CsHs) 1N-CH1(EH(C Hz) alFg (lluHii CHFcmQwmMOwmnsm (Hi) l l on outitcmcisr, CH3

produces a mixture of compounds of formula D, namely v/ (ll t HO--CCHCHlCHlSiFI a( a)a /N 3 CH: CaHs C: and

HKCHz): OH: CH; N--C CHCHzCHQAiF,

and the reaction of gives a mixture of compounds of formula D, namely:

CGHli H: and

Cu Hl The epoxy-organofluorosilanes of this invention and thederivatives produced by the reaction of secondary amines therewith areuseful as sizing and finishing agents for glass fibers. For example,compounds of formula A or of formula D can be employed as sizes forglass roving or yarn in order to reduce damage to the fibers caused bythe fibers rubbing against each other. Also, the compounds of formula Aor formula D can be used as finishes for glass cloth where the glasscloth is used in conjunction with thermosetting organic resins toproduce composite articles.

Glass cloth or fibers can be finished with compounds of formulas A or Dby applying a finishing solution containing the compounds to the clothor fibers and evaporating the solvent. Useful solvents include, forexample, the aliphatic oxygencontaining compounds such as the alkanolsand the ether-alkanols, examples of which include ethanol, propanol,methoxyethanol, ethoxyethanol, and the like, and the aromatichydrocarbons such as benzene, toluene, xylene and the like. Thepreferred solvents are those nonflammable solvents such as water andthose aqueous organic admixtures in which the organic constituent is asolvent for, but nonreactive with. the silane of formula A or D andmiscible with sufficient water as to provide a homogeneous mixturetherewith. The aqueous organic admixtures can contain, for example, fromzero to about 60 parts water and from to 40 parts of an aliphaticoxygen-containing organic compound such as ethanol. Mixtures containing33 parts by weight of water and 67 parts by weight of an alcohol (suchas methanol or ethanol) are particularly useful solvents in thesefinishing solutions. The finishing solution can contain from 0.2 part to5 parts or more by weight of a silane of formulas A or D per 100 partsby weight of the solvent but preferably the solution contains from 1.5parts by weight of the silane per lOO parts by weight of the solution.

When in aqueous solution the silicon-bonded fluorine atoms and/orsilicon-bonded hydrocarbyloxy groups of the silanes of formulas A or Dhydrolyze at a slow rate and, should such solutions be allowed to standfor a sufficiently long period, the silanes are converted to thecorresponding polysiloxanes by hydrolysis and condensation. Admixturesof such polysiloxanes with aqueous organic compounds or with water canbe employed as sizes for glass fiber rovings or finishes for glasscloth. Thus, fibrous glass, glass cloth and the like which has beentreated with such solutions of the silanes of formulas A or D is sizedor finished with the hydrolysis products of these novelorganofluorosilanes.

Finishing solutions containing the compounds of formulas A or D can beapplied to glass cloth by any suitable means (e.g., by spraying orbrushing the solution on the cloth). Preferably, the column is appliedto the cloth by immersing the cloth in the solution and then out theexcess solution by passing the cloth through squeeze rolls. After thefinishing solution is applied to the cloth, the solvent can bevolatilized by air drying the cloth at room temperature. Altemately thefibers can be heated from l00 C. to 200 C. for one to ten minutes topromote the volatilization of the solvent in less time than is requiredfor air drying.

Laminated products can be produced from glass cloth that is finishedwith compounds of formulas A or D by standard procedures. Theselaminates comprise a unitary structure of multiple plies of finishedglass cloth bonded together by an organic resin which has been thermosetby the application of heat. Thus, a layer of finished cloth can becoated or impregnated with a thermosetting organic resin and the processrepeated until an intermediate product of the desired thickness composedof multiple layers of resin-impregnated cloth is produced. Theintermediate product can be converted to or cured to produce a bonded,unitary laminate by heating the intermediate product at a curetemperature from room temperature to about 210 C. The particular curetemperature and cure time employed can vary somewhat depending upon thetype of thermosetting organic resin being used. The curing can beconducted while subjecting the intermediate product to pressure in asuitable apparatus (e.g., in a hydraulic press).

Thermosetting organic resins that are suitable for use in producinglaminated products with glass cloth that is finished with the compoundsof formulas A or D include melamine (melamine-aldehyde) resins, epoxyresins, phenolic (phenolaldehyde) resins, and polyester resins. Suitablethermosetting resins include the phenol-formaldehyde resins, thephenolacetaldehyde resins, the phenol-furfural resins, thecresol-formaldehyde resins, and the melamineformaldehyde resins. Also ofconsiderable interest are the epoxy resins which comprise the diglycidylethers of polyhydric phenols (or polyhydric aliphatic alcohols) as wellas blends of such diglycidyl ethers of polyhydric phenols with suchmodifying ingredients as the polyphenol compounds.

The chemical nature and physical properties of these common laminatingresins and the use of these resins in the production of glass clothlaminates are well known and understood by persons skilled in the fieldof resin laminates. See for example, Plastics Engineering Handbook,"Reinhold Publishing Corp., New York, 1954, Chapter 6 and R. H.Sonneborn, Fiberglas Reinforced Plastics," Reinhold Publishing Corp.,New York, 1954.

The following illustrative examples are presented. ln the examples,b.p." represents boiling point (at one atmosphere pressure unlessotherwise indicated). "n represents refractive index at 25 C. Withreference to the sodium D line, "mm. Hg is the pressure in millimetersof mercury, and NE" represents neutralization equivalent.

EXAMPLE I Into a l-liter, three-necked flask fitted with magneticstirring bar, solid carbon dioxide condenser, gas inlet tube andthermometer was charged 1 14 g. (1.0 moles) of allyl glycidyl etherdissolved in 200 g. of dry tetrahydrofuran and 0.5 g. of achloroplatinic acid solution in ethylene glycol dimethyl ethercontaining 0.0143 g. Pt/g. of solution (calculated to be 20 ppm. Pt).Purified gaseous Cl-l siHF 82 g. (1 mole), was introduced over 0.5 hourwith stirring at room temperature. The reaction was exothermic duringthe first third of addition to about 35 C. Heat was applied to keep themixture at 45 to 55 C. for the balance of the addition. Upon completionof the addition, the mixture was stirred 15 minutes and fractionallydistilled through a two-foot Vigreaux column to give 25 g. of recoveredallyl glycidyl ether (22 percent recovery) and 101 g. of crudegamma-glycidoxypropylmethylidifuorosilane: b.p. 52/0.3 mrn. Hg56/0.4 mm.Hg, n 1.4068, NIB-206 (196.2 calc.

Fractional distillation of the crude product through a 8-10 plate columnisolated purified in 50 mole per cent yield: b.p. l03mm. Hg, N 1.4029.

Analysis-Cale. for C H SiO;F (percent): 42.7 C, 7.2 H, 14.3 Si, 19.4 F,196.2 N.E. Found (percent) 42.9 C, 7.3 H, 14.0 Si, 18.0 F, 2011115 N.E.

The identity of the product was further confirmed by infraredspectrographic analysis.

EXAMPLE 2 Following the procedures of Example 1, methyldifluorosilane isintroduced into a stirred mixture comprising 1,2-epoxy-4-pentenedissolved in tetrahydrofuran with platinum on gamma-alumina catalystsuspended in the solution. The reaction mixture is then fractionallydistilled to yield as the the principal product.

EXAMPLE 3 lnto a l-liter, three-necked flask fitted with magneticstirrer, solid carbon dioxide condenser, thermometer and gas inlet tubeconnected to a tared reservoir of methyldifluorosilane was charged 100g. (0.8 mole) of redistilled vinyl-cyclohexene monoepoxide, 200 ml. ofdried tetrahydrofuran and 6-7 p.p.m. Pt (added as a solution ofchloroplatinic acid in ethylene glycol dimethyl ether). Taking care toexclude moisture, methyldifluorosilane was evaporated into the system atroom temperature over a 1.25 hour period, the reaction mixture beingheld below 57 C. The colorless reaction mixture was fractionallydistilled through a two-foot Vigreaux column to give 26 g. of recoveredstarting olefin and 79 g. of crude epoxyorganofluorosilane product: b.p.54/0.l mrn. Hg62/0.3 mm. Hg, m, 1.435], NE-236-253.

Fractional distillation of the crude product through a l-foot highpacked column gave 65.3 g. (40 mole-percent yield) of purified CH3 Ulla1 CH CHCHQCHgSlFj 1 CH /CH:

EXAMPLE4 Into a 500 ml. distillation flask fitted with condenser, dryingtube, thermometer and heating mantle was charged 90 g. (0.45 moles) ofgamma-glycidoxypropylmethyldifluorosilane (2.0 moles) of drieddiisopropylamine and 2 drops of ethanol. The mixture was heated for 64hours at -90 C., cooled to 10 C. and filtered. The filtrate wasfractionally distilled to give 40.5 g. (.136 moles) of b.p. 77 C./.02mm. Hg97 C./.l0 mm. Hg, n,, 1.4422, a 30 mole percent yield:

The identity of the product was confirmed by elemental and infraredspectrographic analysis.

Results of elemental analysis:

Calc. for 'C H SiO NF (percent): 52.5 C, 9 9.4 Si, 4.7 N, 297.6 N.E.Found: 53.4 c, 9.6 H, 9. 4.6 N, 298 N.E.

What is claimed is: l. Epoxyorganofluorosilanes represented by theformula wherein Y is a substituted monovalent hydrocarbon group free ofaliphatic unsaturation in which said substitution is an oxirane ring,and having from three to about ten carbon atoms; R is a monovalenthydrocarbon group free of aliphatic unsaturation and having from one toabout ten carbon atoms; X is selected from the class consisting offluorine and hydrocarbyloxy groups OR; 17 is an integer having a valuefrom zero to l; c is an integer having a value from 1 to 2; d is aninteger having a value from zero to 1; the sum of c and a is 2; when bis zero then e is an integer having a value from 1 to about 6, and whenb is 1 then (i) e is an integer having a value from 2 to about 6 and theoxygen atom is separated from silicon by at least two carbon atoms ofthe C,.H group and (ii) the oxirane ring in the Y group is separatedfrom the oxygen atom by at least one carbon atom.

2. The epoxyorganofluorosilanes in accordance with claim 1 wherein R isthe methyl group, X is fluorine, c is l and dis 1.

3. The compound represented by the formula UNITED STATES PATENT OFFICECERTIFICATE OF CORRECTION Patent No. 3 624 109 Dated N h 3 192] I t iscert] find that error appears In the shove-IdenL i I led mu-n1 and thatsaid Letters Patent are hereby corrected as shown below:

Column 1, line 23; After "d" delete --carbon-- Column 3, first formula;"C1 should read --Cl Column 5, line 31; "H3CH2CH2CHFH-CH2-" should read--CH3CH2CH2-C'2H-(.3H-CH2- Column 5, line 60; Delete second appearingThe--.

Column 8, line 40, "column" should read "solution-- line 41; After"then" insert --squeezing-- Column 9, line 45; "103mm" should read--l03/l7mm-- Signed and Sealed this 1 7th -fl. .y of JepfeInlw-r !,C7"+.

(SEhL) fittest:

MCCOY M. GIBSON JR. C. MARSHALL DANN Attesting Officer Commissioner ofPatents PC4050 0459) uscoMM-oc B0376-F69

2. The epoxyorganofluorosilanes in accordance with claim 1 wherein R isthe methyl group, X is fluorine, c is 1 and d is
 1. 3. The compoundrepresented by the formula
 4. The compound represented by the formula